Alkylene oxide adducts of n-alkylcyclohexyl-1, 3-propanediamines



3,378,503 Patented Apr. 16, 1968 United States Patent Ofi ice ide. The availability of three reactive sites allows greater 3,378,503 flexibility in the properties of the final product. The three ALKYLENE OXIDE ADDUCTS F N-ALKYL- CYCLOHEXYL-1,3-PROPANEDIAMINES George P. Sperauza and Ernest L. Yeakey, Austin, Tex.,

asslgnors to Jefferson Chemical Company, Inc., Houston, Tex., a corporation of Delaware No Drawing. Filed Oct. 21., 1964, Ser. No. 405,573 10 Claims. (Cl. 260-2) amino hydrogen atoms are sufficiently reactive that each will react with one mol of an epoxide without the use or" an extraneous catalyst. In order to add more than three mols of oxide, an alkoxylation catalyst as described hereinbelow is required. From about 0.01 to about 5 Wt. percent of catalyst should be used, based on the weight of alkylcyclohexylpropylenediamine employed. The three mol adducts may be isolated and used as starting materials to prepare the higher adducts or higher adducts may be prepared directly from the N-alkylcyclohexyl-1,3- propanediamines.

Examples of alkoxylation catalysts are well known to those skilled in the art. Generally, these fall into three categories: alkaline, neutral and acid. The alkaline and neutral catalysts are the most suitable for our process. Alkaline catalysts include the alkali metals, alkali metal Wherelh R 4 14 alkyl g p, 15 Selected from the hydroxides, alkaline earth metal hydroxides and quatergfOuP eoflslshng of hydrogen, methyl, ethyl, ChlOTO' nary ammonium hydroxides. Suitable neutral catalysts inmethyl, and mixtures thereof, and the Sum of X P y elude neutral salts such as alkali metal halides and qua- P Z is 1 to ternary ammonium halides. Specific catalysts that can be The adducts are useful as detergents d 215 P l used include, for example, sodium, sodium hydroxide, termedietes in the Preparfllieh of Polyurethane foampotassium hydroxide, calcium hydroxide, barium hydrox- Also, they may be reacted With diePOXideS Provide ide, benzyltrimethylammonium hydroxide, lithium chloresinous mixtures in the preparation of coatings and adride, potassium b i d h h i h l i heslvesbromide. Preferred catalysts are sodium hydroxide and potassium hydroxide.

This invention is concerned with adducts of alkylcyclo- Alkylene OXideS that y be reacted Wiih active y hexylpropylenediamihes Mare particularly, i i ti gen compounds are also well known to those skilled in the is concerned with novel alkylene oxide addition products t a include both IhOflO- and diePOXideS- Suitable of alkylcyclohexylpropylenediamines and a method for m p xi fer eXamP1e,lhSe haiing the formula: their preparation. 0

Alkylene oxide adducts of fatty amines are well known wherein R is selected from the group consisting of hyand widely used in the detergent, paper, textile, plastics, rubber and paint industries. Further, in copending application Ser. No. 405,615, filed of an even date herewith, drosen, r w alkyl, Phenyl, chlorpmethyl and Y q Y- there are disclosed alkylene oxide adducts of alkylcyclomethyl- Exefhples of Shell eP0 XideS Include ethylene hexylaminfis propylene oxide, but yiene oxide, dodecene oxlde, styrene We have now discovered that valuable amine com- OXlde; elilehl'ofohydflhhhd y h pounds may be obtained by the addition of alkylene ox- Sultable dleppXldqs f e buiadlehe l ei y ides to N-alkylcyclohexyl-1,3-propanediamines. Tailored eyelohexehe lf' i chylnylbehzene dleleoxlde e products h i id l varying properties may b h. various polymeric mater1als term1nated with epoxide tained by proper choice of the N-alkylcyciohexyl-1,3- p Such Polymeric materials are, for p those propanediamine and al-kylene oxide employed F 0 obtained by the condensation polymerization of epichloroabout 1 to about 100 mols of alkylene oxide are reacted hydrin with bisphenol-A whereby there are obtained with the N-alkylcyclohexyl-1,3-propanediamine at a tempolymers having the formula:

ABSTRACT OF THE DISCLOSURE A product having the formula:

(oII20Ho H N'CH2CH2CH2N R R Hz(]JHO),-H oHu JHo),H

/O\ CH3 IOH CH3 /O\ out-oH-ont-[-o s--o-ornonom- ..0 +-0-orn- :H-om

33113 CH3 perature within the range of from about to about wherein n is within the range of from about 0 to 8. An- 200 C. other polymeric diepoxide is that obtained by the reaction The N-alkylcyclohexyl-l,B-propanediamine starting maof epichlorohydrin with a polyglycol to give products terial for my invention is one having the formula: having the formula:

Drenornorncnmrn CH2-CHCH2O(CHCH2-O)mCH2 CH-CH2 wherein R is a C C alkyl group. The alkyl group may be a branched or straight-chain alkyl group, the choice of groups depending upon the properties desired in the final n a product. For example, if a biologically soft surface-active i g of i f y g :23 agent is desired, a straight-chain alkyl group should be W fi' i f ga i ursba 2 Th employed. The alkyl group may be attached to the ring at l fihv d range 0 a on i b o ta1 861 t a t. 50 any position other than the number one position. As a pie emperfnure range f o practical matter, the N alkylcyclohcxyhlfihropanedif When a volatile alkylene ox de 13 employed, the reacamine employed will probably be a mixture f isomers trons are normally conducted in a closed vessel at the i the 44 predominating ambient pressure at the particular temperature employed.

The Nalkylcyclohexyl-1,3-propanediamine starting ma- At the Completion of the reaction, it y be desirable terials of the present invention have three reactive amino to remove the catalyst. Neutral catalysts may Often be hydrogen atoms, all of which react with the alkylene oxremoved simply by filtration. Alkaline catalysts may be wherein m is from 1 to about 200 and R" may be hydrogen, a C -C alkyl group or a phenyl group.

4 neutralized and the salts removed by filtration. Acids that propylene oxide, butylene oxide, epichlorohydrin, and may be used to neutralize alkaline catalysts include phosmixtures thereof. Such products have the formula: phoric, sulfuric, acetic, carbon dioxide and solid organic n acids as described in United States Patent 3,000,963.

The following specific examples are illustrative of our invention but are not intended to limit the scope of the R r gn cr-rmrn (CH CHO) -1I invention in any respect.

Example I wherein R is a C C alkyl group, R is selected from the group consisting of hydrogen, methyl, ethyl and chloromethyl groups, and the sum of x plus y plus z is from 1 to 100.

Cross-linking results when diepoxides are used, thereby resulting in very complex mixtures. These resinous mix- 15 tures are useful in the preparation of coatings and adhesives.

Having thus described our invention, we claim:

The three-mol ethylene oxide adduct of N-nonyl- 10 cyclohexyl-l,3-propanediamine was prepared in the following manner. To a one-liter stirred autoclave was added 367 g. (1.3 mols) of nonylcyclohexyl-1,3-propanediamine. The autoclave was flushed twice with nitrogen, ml. of ethylene oxide was added and the mixture Was heated to 96 C. at which point a reduction in pressure was noted. An additional 179 g. of ethylene oxide was added at 96 to 110 C. over a three-hour A Product havmg the formula: period. The reaction mixture was digested for an addi- (CHzCHO)x-H tional hour at 100 C. The product was a clear red liquid 20 O I which was insoluble in water.

R H2CHO)ZH (CI-IzCHO) H Example 11 L The three-mol propylene oxide adduct of N-nonylwherein R is a alkyl group- R' is lect d fr m cyclohexyl-1,3-propanediamine was prepared as follows: 5 the group consisting of hydrogen, methyl, ethyl, chloro- To a one-liter stirred flask were added 141 g. (0.5 mol) yl, n mix ure hereof, and the sum of x plus y of nonylcyclohexyl 1,3 propanediamine, 160 g. of plus 1 is 1 to 100. methanol and 14 ml. of water. The solution was heated 2. A product as in claim 1 wherein R is hydrogen. to 65 C. and propylene oxide addition was started. After 3. A product as in claim 1 wherein R is methyl.

1.5 mols of propylene oxide was added, the mixture was 4- A method for the preparation of an alkylene oxide digested for one hour at 65 C. The solution was light addition product which comprises adding from 1 to about yellow. The solvent was evaporated to a pot temperature 100 mols of an alkylene oxide having the formula: of 150 C. at a reduced pressure of about 30 mm. The product was a viscous but pourable liquid that was soluble in acetone and insoluble in water. R

wherein R is selected from the group consisting of hydro- Example In gen, C1-C1g allkyl, phenyl, chloromethyl, hydroxmethyl,

and mixtures thereof, to an N-alkylcyclohexyl-1,3-pro- The mne-mol ethylene oxide adduct of N-nonylcyclopanediamine having the formula:

hexyl-1,3-propanediamine was prepared in the following 40 way. To a one-liter stirred autoclave were added 141 g. of nonyl-cyclohexyl-1,3-propanediamine (0.5 mol) and @NHCHZCHZCHZNHZ 0.71 g. of potassium hydroxide. The autoclave was R flushed twice with nitrogen and 20 m1. of ethylene oxide wherein R is a C C alkyl group at a temperature withwas added. The contents were heated to 127 C. and in the range f about to about 200 C. in the resadditional ethylene oxide was added as it reacted at ence of from about 0.01 to about 5 wt. percent of an al- 127132 C. A total of 193 g. or 4.5 mols of ethylene koxylation catalyst based on the weight of N-alkylcyclooxide were added over a four-hour period. The contents hexyl-LB-propanediamine employed, said alkoxylation were digested for an additional thirty minutes at 130 C. catalyst being selected from the group consisting of alkali The product was a clear red liquid that exhibited good 50 metals, alkali metal hydroxides, alkaline earth metal hyfoaming properties. droxides, quaternary ammonium hydroxides, alkali metal halides and quaternary ammonium halides. Emmp 16 IV 5. A method as in claim 4 wherein the alkylene oxide The three-mol ethylene oxide adduct of dodccylis ethylene oxide.

cyclohexyl-l,3-propanediamine was prepared in the 6. A method as in claim 4 wherein the alkylcne oxide following way. To a 600 ml. shaker-type autoclave were is propylene oxide. added 50 g. of N-dodecyclohexyl-l,3-propanediamine, 7. A method as in claim 4 wherein one-three mols of 150 g. of methanol and 7 g. of water. The autoclave was alkylene oxide are added without the use of an alkoxylaflushed twice with nitrogen and 25 ml. of ethylene oxide tion catalyst. was added. The reaction mixture was heated to 100 C. 8. A method for the preparation of an epoxide addiand held at this temperature for two hours. The methanol tion product which comprises adding from 1 to about and water were removed to a pot temperature of 200 C. mols of a dicpoxide selected from the group consisting of at atmospheric pressure and then to a pot temperature of butadiene diepoxide, vinylcyclohexene diepoxide, divinyl- C. at 1 mm. pressure. The product was a clear amber benzene diepoxide, and polymeric diepoxides having the liquid insoluble in water and slightly soluble in acetone formulas:

and cyclohexane. It had an equivalent weight of 230 (Theory 229).

The novel adducts of the present invention are useful CHtOHCHr-O(CHCH: )m-CHzCH-CH: as detergents and as polyol intermediates in the preparation of polyurethane foams. The preferred mono-epoxide addition products are those obtained from ethylene oxide, 75 wherein n is from 0 to about 8, m is from 1 to about 200 @n-ncmomonmm wherein R is a C C alkyl group at a temperature within the range of about 50 to about 200 C. in the presence of from about 0.01 to about 5 wt. percent of an alkoxylation catalyst based on the weight of N-alkylcycl'ohexyl- 1,3-propanediamine employed, said alkoxylation catalyst being selected from the group consisting of alkali metals, alkali metal hydroxides, alkaline earth metal hydroxides,

quaternary ammonium hydroxides, alkali metal halides and quaternary ammonium halides.

9. A method as in claim 8 wherein one-three mols of diepoxide are added without the use of a catalyst.

10. A product prepared by the method of claim 8.

References Cited UNITED STATES PATENTS 4/1963 Currier et a1. 260-563 WILLIAM H. SHORT, Primary Examiner. T. D. KERWIN, Assistant Examiner. 

